Thiophene Azo Dyes and Laundry Care Compositions Containing the Same

ABSTRACT

This application relates to thiophene azo dyes for use as hueing agents, laundry care compositions comprising such thiophene azo dyes, processes for making such thiophene azo dyes, and laundry care compositions and methods of using the same. The thiophene azo dyes contain a formally charged moiety and are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades. These thiophene azo dyes are advantageous in providing a hueing effect, for example, a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics. The thiophene azo dyes are also generally stable to bleaching agents used in laundry care compositions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/412,897, entitled “Thiophene Azo Dyes and Laundry CareCompositions Containing the Same,” which was filed on Nov. 12, 2010, andis entirely incorporated by reference herein.

TECHNICAL FIELD

This application relates to thiophene azo dyes for use as hueing agents,laundry care compositions comprising such thiophene azo dyes, processesfor making such thiophene azo dyes and laundry care compositions andmethods of using the same. The aforementioned thiophene azo dyes containa formally charged moiety and are generally comprised of at least twocomponents: at least one chromophore component and at least onepolymeric component. Suitable chromophore components generally fluoresceblue, red, violet, or purple color when exposed to ultraviolet light, orthey may absorb light to reflect these same shades. These thiophene azodyes are advantageous in providing a hueing effect, for example, awhitening effect to fabrics, while not building up over time and causingundesirable blue discoloration to the treated fabrics. The thiophene azodyes are also generally stable to bleaching agents used in laundry carecompositions.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. Thus, the purpose of hueing agents is generallyto visually brighten these textile substrates and counteract the fadingand yellowing of the substrates. Typically, hueing agents may be foundin laundry detergents, fabric softeners, or rinse aids and are thereforeapplied to textile substrates during the laundering process. However, itis important that hueing agents function to visually brighten treatedtextile substrates without causing undesirable staining of the textilesubstrates. Cellulosic substrates, in particular, tend to exhibit ayellow hue after exposure to light, air, and/or soiling. This yellownessis often difficult to reverse by normal laundering procedures. As aresult, there exists a need for improved hueing agents which are capableof eliminating the yellowness exhibited by ageing cellulosic substrates.By utilizing such improved hueing agents, the life of the textilesubstrates, such as clothing articles, table linens, etc., may beextended. Unfortunately, current hueing agents either do not provide ahueing benefit after a single treatment cycle and/or they build up to anundesirable level, thus overhueing the treated situs over multipletreatment cycles.

The hueing agents disclosed herein and the laundry care compositionscomprising same offer advantages over previous efforts in this area, as,unlike previous thiophene azo hueing agents, the present hueing agentscomprise a formally charged moiety that allows such hueing agents toprovide enhanced deposition, removal and hue angle when used incompositions such as laundry care compositions. In addition to theenhanced deposition, removal and hue angle, the present hueing agentsoffer improved stability in wash environments that contain bleachingagents, for example bleach boosters. While not being bound by theory,Applicants believe that such enhanced stability is, at least in part,due to the improved partitioning behavior of such hueing agents. Theaforementioned benefits are offered over a range of fabric types. Inshort, Applicants recognized the source of the current hueingdeficiencies and herein provide the solution to such problem. The hueingcompounds disclosed herein also absorb light at a wavelength appropriateto visually neutralize the yellowness of substrates, including textilesubstrates. These compounds function ideally as hueing agents forsubstrates, including textile substrates, and may be incorporated intolaundry care compositions for use by consumers.

SUMMARY OF INVENTION

This application relates to thiophene azo dyes for use as hueing agents,laundry care compositions comprising such thiophene azo dyes that mayserve as hueing agents, processes for making such thiophene azo dyes andlaundry care compositions and methods of using the same. Theaforementioned thiophene azo dyes contain a formally charged moiety andare generally comprised of at least two components: at least onechromophore component and at least one polymeric component. Suitablechromophore components generally fluoresce blue, red, violet, or purplecolor when exposed to ultraviolet light, or they may absorb light toreflect these same shades. These thiophene azo dyes are advantageous inproviding a hueing effect, for example, a whitening effect to fabrics,while not building up over time and causing undesirable bluediscoloration to the treated fabrics. The thiophene azo dyes are alsogenerally stable to bleaching agents used in laundry care compositions.

DETAILED DESCRIPTION

As used herein, the term “alkoxy” is intended to include C₁-C₈ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the terms “alkyl” and “alkyl capped” are intended toinclude C₁-C₁₈ alkyl groups, and in one aspect, C₁-C₆ alkyl groups.

As used herein, the term “aryl” is intended to include C₃-C₁₂ arylgroups.

As used herein, the term “arylalkyl” is intended to include C₁-C₁₈ alkylgroups and, in one aspect, C₁-C₆ alkyl groups.

As used herein, the term “formally charged moiety” means a moiety havingat least one formal positive charge or at least one formal negativecharge in aqueous solution at a pH in the range from 7 to 11.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose barform and/or flake type washing agents and/or fabric treatmentcompositions.

As used herein, the term “fabric treatment composition” includes, unlessotherwise indicated, fabric softening compositions, fabric enhancingcompositions, fabric freshening compositions and combinations there of.Such compositions may be, but need not be rinse added compositions.

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, the articles including “the”, “a” and “an” when used ina claim, are understood to mean one or more of what is claimed ordescribed.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

As used herein, the term “maximum extinction coefficient” is intended todescribe the molar extinction coefficient at the maximum wavelength inthe range of 400 nanometers to 750 nanometers.

As a consequence of their manufacturing process, the thiophene azo dyesdisclosed herein may contain a distribution of repeating units in theirpolymeric moiety. Accordingly, in one aspect, the molecular weight ofthe thiophene azo dyes disclosed herein may be reported as an averagemolecular weight, as determined by its molecular weight distribution.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

Suitable Hueing Agents

The hueing agents of the present invention include thiophene azo dyeswhich contain a formally charged moiety. However, these thiophene azodyes do not comprise a meta-bis(2-hydroxy-3-trimethylammoniumpropyl)amino tolyl group.

In one aspect, the aforementioned thiophene azo dyes comprise athiophene moiety, an azo moiety and a coupler moiety, said thiophenemoiety being covalently bound to said azo moiety and said coupler beingcovalently bound to said azo moiety, at least one of said thiopheneand/or azo moieties comprising a formally charged moiety.

The hueing agents of the present invention may be dyes, pigments, orpolymeric colorants generally comprising a chromophore constituent and apolymeric constituent. The chromophore constituent is characterized inthat it emits or absorbs wavelength in the range of blue, red, violet,purple, or combinations thereof upon exposure to light. In one aspect,the chromophore constituent exhibits an absorbance spectrum maximum inthe wavelength range of about 400 nanometers to about 750 nanometers, inanother aspect of about 520 nanometers to about 650 nanometers, in yetanother aspect of about 540 nanometers to about 630 nanometers, inanother aspect of about 560 nanometers to about 610 nanometers, inanother aspect of about 565 nanometers to about 580 nanometers inmethanol solution.

Examples of suitable polymeric constituents include polyoxyalkylenechains having multiple repeating units. In one aspect, the polymericconstituents include polyoxyalkylene chains having from 2 to about 30repeating units, from 2 to about 20 repeating units, from 2 to about 10repeating units or even from about 3 or 4 to about 6 repeating units.Non-limiting examples of polyoxyalkylene chains include ethylene oxide,propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.

In one aspect of the invention, the thiophene azo dye contains aformally charged moiety, with the proviso that the dye does not comprisea meta-bis(2-hydroxy-3-trimethylammoniumpropyl) amino tolyl group. Thethiophene azo dye exhibits, in the wavelength range of about 400 nm toabout 750 nm in methanol solution, or of about 520 nm to about 650 nm inmethanol solution, or of about 540 nm to about 630 nm in methanolsolution, or of about 560 nm to about 610 nm in methanol solution, or ofabout 565 nm to about 580 nm in methanol solution, a maximum extinctioncoefficient from about 1000 to about 1,000,000 liter/mol/cm, or fromabout 5,000 to about 750,000 liter/mol/cm, or from about 10,000 to about500,000 liter/mol/cm, or from about 20,000 to about 250,000liter/mol/cm. The thiophene azo dye exhibits a molecular weight fromgreater than 300 daltons, or from about 300 daltons to about 5000daltons, or from about 350 daltons to about 3000 daltons, or from about400 daltons to about 1500 daltons. The thiophene azo dye exhibits anaqueous partition value from about 10% to 100% or from about 20% to 100%or from about 30% to 100% or from about 40% to 100%, said dye comprisinga non-covalently bound charge balancing counterion. The thiophene azodye further exhibits an aqueous partition value from 0% to about 40%,from 0% to about 30%, from 0% to about 20%, or from about 1% to about10%, said dye comprising a covalently bound charge balancing counterion.

The thiophene azo dye of the present invention may be represented bygeneral Formula (I):

-   -   wherein:        -   a.) R₁, R₂ and R₃ are each independently selected from            hydrogen, electron-withdrawing moieties, and            electron-donating moieties, provided that at least one of            R₁, R₂ and R₃ is an electron-withdrawing moiety; in another            aspect, R₁ is an electron-withdrawing moiety; in yet another            aspect, R₁ and R₃ are electron-withdrawing moieties; and        -   b.) wherein X is an organic moiety having a molecular weight            from about 65 daltons to about 4855 daltons, or from about            150 daltons to about 2855 daltons, or from about 193 daltons            to about 1355 daltons, or from about 300 daltons to about            855 daltons, or from about 400 daltons to about 600 daltons,            or from about 420 daltons to about 575 daltons.

In yet another aspect of the thiophene azo dye, each R₁, R₂ and R₃ maybe independently selected from hydrogen, (C₁-C₄)-alkyl, (C₃-C₁₀)-aryl,carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro,(C₁-C₄)-alkyl ester, halogen or amino moiety, or each R₁, R₂ and R₃ maybe independently selected from hydrogen, nitro, cyano, (C₁-C₄)-alkylester or (C₁-C₄)-alkyl.

In a further aspect of the thiophene azo dye, the X may be a moietyhaving Formula (II) below:

-   -   wherein:        -   i.) R₄ is selected from a moiety having Formula (III) below

-   -   -   -   wherein:            -   i.) Each R₈ is independently selected from hydrogen,                C₁-C₈ alkyl optionally substituted with a hydroxy, or                acetyl;            -   ii.) m is an integer from 0 to 10;            -   iii.) Y is selected from a sulfonate, carboxylate, a                phosphonate or quaternary ammonium species selected from                an imidazolium, pyridinium, morpholinium, piperidinium,                or a moiety having Formula (IV) below:

-   -   -   -   -   wherein:                -   i.) R₉ is a C₁-C₈ alkyl moiety optionally                    substituted with —OH,                -   ii.) R₁₀ is selected from C₁-C₁₈ alkyl moiety                    optionally substituted with —OH, or C₂-C₈ alkyl                    substituted with sulfonate, or C₁-C₈ alkyl                    substituted with carboxylate,                -   iii.) Z is a charge balancing counterion of unit                    charge c; the index b is 1 when R₁₀ is a C₁-C₁₈                    alkyl moiety optionally substituted with —OH,                    otherwise the index b=0;

        -   Or, R₄ is selected from a moiety having Formula (V) below:

-   -   -   -   wherein            -   i.) Each R₁₁ and R₁₂ is independently selected from                hydrogen, C₁-C₈ alkyl, aryl, acetyl or hydroxyl moiety;                m and n are independent and are integers from 0 to 10,            -   ii.) Y is as described above;

        -   Or, R₄ is selected from a moiety having Formula (VI) below:

-   -   -   -   wherein            -   i.) R₁₃ is selected from an aryl moiety, arylalkyl                moiety such as a benzyl moiety, C₁-C₁₈ alkyl moiety, or                a siloxane moiety;            -   ii.) Each R₁₄ is independently selected from hydrogen,                C₁-C₄ alkyl; m is an integer from 0 to 10; and            -   iii.) Y is as described above;

        -   ii.) R₅ can be the same as R₄ or selected from C₁-C₁₂ alkyl            moiety, aryl moiety or arylalkyl moiety such as a benzyl            moiety; wherein the index a is an integer from 0 to 4, or            from 0 to 3, or from 0 to 2, and each R₆ may be            independently selected from a C₁-C₆ alkyl, a C₁-C₄ alkoxy, a            nitro, a hydroxyl, a halogen, or —NHC(O)R₂₂ wherein R₂₂ is            selected from H, —NH₂, C₁-C₆ alkyl, phenyl, —(CH₂)_(s)OR₂₃            where the index s is 1 or 2 and R₂₃ is selected from Me,            phenyl, and —CO₂CH₂CN; —NHSO₂R₂₄ wherein R₂₄ is C₁-C₄ alkyl            or phenyl; said alkyl, alkoxy and acetamido moieties may be            optionally substituted with a formally charged moiety;

    -   Or, X is a moiety having Formula VII below:

-   -   wherein each R₄ and R₅ can independently be selected from:    -   a) [(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)R₁₅];    -   b) alkyl, aryl or aryl alkyl;    -   c) [CH₂CH(OR₁₆)CH₂OR₁₇];    -   d) the amino addition product of styrene oxide, glycidyl methyl        ether, isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl        glycidyl ether, 2-ethylhexylgycidyl ether, and glycidylhexadecyl        ether, followed by the addition of from 1 to 10 alkylene oxide        units wherein at least one such alkyleneoxide unit is        substituted with R₁₅ that is not —H;    -   wherein R′ is selected from the group consisting of H, CH₃,        CH₂—O—(CH₂CH₂O)_(z)R₁₅, and mixtures thereof; R″ is selected        from the group consisting of H, CH₂—O—(CH₂CH₂O)_(z)R₁₅, and        mixtures thereof; x+y≦20; y≧1; z=0 to 10; each R₁₅ is        independently selected from —H and —CH₂CHR₁₈N⁺R₁₉R₂₀R₂₁ wherein        R₁₈ is selected from —H and —CH₃; each R₁₉ and R₂₀ is        independently selected from C₁-C₄ alkyl optionally substituted        with —OH; R₂₁ is independently selected from C₁-C₁₂ optionally        —OH substituted alkyl or (CH₂)_(r)O_(p)Q; the index r is an        integer from 1 to 8; the index p is 0 or 1; and wherein Q is an        anionic group selected from —CO₂ ⁻, and —SO₃ ⁻; R₁₆ is selected        from the group consisting of H, (CH₂CH₂O)_(z)R₁₅ wherein z=0 to        10, and mixtures thereof; R₁₇ is selected from the group        consisting of C₁-C₁₆ alkyl, C₆-C₁₀ aryl groups, and mixtures        thereof; the index m is an integer from 0 to 4 and each R₆ is as        defined above; Z is a charge balancing counterion of unit charge        c; the index b is equal to the number of non-H R₁₅ groups that        do not comprise a covalently bound charge balancing counterion;        further provided the molecule contains at least one non-H R₁₅        group.

In a further aspect of the thiophene azo dye, X may be a moiety havingFormula (II) below:

-   -   wherein:        -   i.) R₄ is selected from a moiety having Formula (III) below

-   -   -   -   wherein:            -   i.) R₈ is a hydrogen, C₁-C₄ alkyl moiety or aryl moiety;            -   ii.) Y is a quaternary ammonium species selected from a                group consisting of an imidazolium, or a moiety having                Formula (IV) below:

-   -   -   -   -   wherein:                -   i.) R₉ is a C₁-C₂ alkyl moiety,                -   ii.) R₁₀ is selected from C₁-C₈ alkyl moiety                    optionally substituted with —OH, or C₂-C₄ alkyl                    substituted with sulfonate, or C₁-C₄ alkyl                    substituted with carboxylate,                -   iii.) Z is a charge balancing counterion of unit                    charge c; the index b is 1 when R₁₀ is a C₁-C₈ alkyl                    moiety optionally substituted with —OH, otherwise                    the index b=0;

            -   Or, R₄ is selected from a moiety having Formula (V)                below:

-   -   -   -   wherein            -   i.) Each R₁₁ and R₁₂ is independently selected from                hydrogen, C₁-C₄ alkyl or aryl moiety; m and n are                independent and are integers from 0 to 5,            -   ii.) Y is as described above,            -   Or, R₄ is selected from a moiety having Formula (VI)                below:

-   -   -   -   wherein            -   i.) R₁₃ is selected from an aryl moiety, benzyl moiety,                or a C₁-C₁₈ alkyl moiety;            -   ii.) Each R₁₄ is independently selected from hydrogen or                —CH₃; m is an integer from 0 to 10,

        -   ii.) R₅ can be the same as R₄ or selected from C₁-C₆ alkyl            moiety or benzyl moiety;

        -   iii.) Wherein the index a is an integer from 0 to 2, and            each R₆ may be independently selected from methyl, methoxy,            or acetamido moiety.

In one aspect of the thiophene azo dye of the present invention, eachR₁, R₂ and R₃ may be independently selected from hydrogen,(C₁-C₄)-alkyl, (C₃-C₁₀)-aryl, carboxylate, cyano, sulfonate,phosphonate, sulfate, acetate, nitro, (C₁-C₄)-alkyl ester, halogen oramino moiety, or each R₁, R₂ and R₃ may be independently selected fromhydrogen, nitro, cyano, (C₁-C₄)-alkyl ester or (C₁-C₄)-alkyl.

In yet a further aspect, the thiophene azo dye of the present inventionmay be represented by Formula (VIII):

A-N═N—X  Formula VIII

wherein the A moiety is selected from the group consisting of Table 1AMoieties Nos. 1-118, or Table 1A Moieties Nos. 6-11, 15, 21-23, 30-31,33-39, 41, 43, 46-48, 50-55, 57-58, 64-65, 70-73, 77-78, 82-86, 88-90,93-95, 99-100, 104-106, and 110-118, or Table 1A Moieties Nos. 9-11, 15,23, 34-35, 37-39, 41, 43, 47, 50-51, 57-58, 77, 83, 89, 95, 106, and110-118; and wherein the X moiety is selected from the group consistingof Table 4X Moieties Nos. 1-31.

In yet another aspect, the thiophene azo dye of the present inventionmay be represented by

wherein the moiety A is selected from Table 1A Moieties Nos. 1-118, orfrom Table 1A Moieties Nos. 6-11, 15, 21-23, 30-31, 33-39, 41, 43,46-48, 50-55, 57-58, 64-65, 70-73, 77-78, 82-86, 88-90, 93-95, 99-100,104-106, and 110-118, or from Table 1A Moieties Nos. 9-11, 15, 23,34-35, 37-39, 41, 43, 47, 50-51, 57-58, 77, 83, 89, 95, 106, and110-118; a=0 to 2; when a=1 or 2, R₆ is selected from Table 2 R₆Substituent Identity and Position Nos. 1-40, or from Table 2 R₆Substituent Identity and Position Nos. 1, 3, 5, 7-9, 11-14, 21, 23-24,31, 33-34, 36 and 40, or from Table 2 R₆ Substituent Identity andPosition Nos. 1, 3, 5, 7, 12, 13, 14, 31, 36 and 40; and R₄ and R₅grouping is selected from Table 3 R₄ and R₅ Groupings Nos. 1-69, or fromTable 3 R₄ and R₅ Groupings Nos. 3-6, 10, 13-14, 17-21, 23-24, 27-28,31-35, 37-38, 41, 44-49, 51-52, 54-56, 58, 60-69, or from Table 3 R₄ andR₅ Groupings Nos. 3, 5-6, 10, 13-14, 17, 19-21, 24, 27-28, 31-34, 38,41, 44-48, 52, 54-55, 58, 60-64 and 69.

A moieties may be selected from the moieties shown in Table 1:

TABLE 1 A Moieties No. A  1

 2

 3

 4

 5

 6

 7

 8

 9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100 

101 

102 

103 

104 

105 

106 

107 

108 

109 

110 

111 

112 

113 

114 

115 

116 

117 

118 

R₆ may be selected from the substituents shown in Table 2:

TABLE 2 R₆ Substituent - Identity and Position

R₆ Substituent - Identity and Position on Aniline Ring No. 1 2 3 4  1—OH  2 —Cl —OH  3 —OMe —OH  4 —On-Bu —OH  5 —Me  6 —Me —Me  7 —OMe —Me 8 —OEt —Me  9 —Cl 10 —Br 11 —NO₂ 12 —NH₂ 13 —NHAc 14 —OMe —NHAc 15—NHC(O)Et 16 —OMe —NHC(O)Et 17 —OEt —NHC(O)Et 18 —NHC(O)n-Pr 19 —Me—NHC(O)n-Pr 20 —NHC(O)i-Pr 21 —NHC(O)n-Bu 22 —OMe —NHC(O)n-Bu 23—NHC(O)c-C₆H₁₁ 24 —NHC(O)Ph 25 —OMe —NHC(O)Ph 26 —NHC(O)CH₂OMe 27—NHC(O)CH₂OPh 28 —NHC(O)CH₂CH₂OMe 29 —NHC(O)CH₂CH₂OEt 30—NHC(O)(CH₂)₂CO₂CH₂CN 31 —NHC(O)NH₂ 32 —NHSO₂Me 33 —NHSO₂Et 34 —OMe—NHSO₂Et 35 —NHSO₂Ph 36 —OMe 37 —Me 38 —Cl 39 —NO₂ 40 —OMe —OMe

R₄ and R₅ groupings may be selected from the groupings shown in Table 3:

TABLE 3 R₄ and R₅ Groupings No. R₄ R₅  1 Ethyl

 2 Ethyl

 3 Ethyl

 4 Ethyl

 5 Ethyl

 6 Ethyl

 7 Ethyl

 8 Ethyl

 9 Ethyl

10 Ethyl

11 Ethyl

12 Ethyl

13 Ethyl

14 Ethyl

15 Benzyl

16 Benzyl

17 Benzyl

18 Benzyl

19 Benzyl

20 Benzyl

21 Benzyl

22 Benzyl

23 Benzyl

24 Benzyl

25 Benzyl

26 Benzyl

27 Benzyl

28 Benzyl

29 Hexyl

30 Hexyl

31 Hexyl

32 Hexyl

33 Hexyl

34 Hexyl

35 Hexyl

36 Hexyl

37 Hexyl

38 Hexyl

39 Hexyl

40 Hexyl

41 Hexyl

42 Isopropyl

43 Isopropyl

44 Isopropyl

45 Isopropyl

46 Isopropyl

47 Isopropyl

48 Isopropyl

49 Isopropyl

50 Isopropyl

51 Isopropyl

52 Isopropyl

53 Isopropyl

54 Isopropyl

55

56

57

58

59

60

61

62

63

64

65 Ethyl

66 Benzyl

67 Isopropyl

68

69

The “*” denotes point of attachment to additional moieties. “Z” denotesthe appropriate charge balancing counterion.

X moieties may be selected from the moieties shown in Table 4:

TABLE 4 X Moieties No. Z = O-Tosylate or Halogen  1

 2

 3

 4

 5

 6

 7

 8

 9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

It is contemplated to be within the scope of this invention that thethiophene azo dye having a formally charged moiety may comprise any oneof the A moieties selected from Table 1, any one of the R₆ substituentsselected from Table 2, any one of the R₄ and R₅ groupings selected fromTable 3, and any one of the X moieties selected from Table 4.

In yet another aspect of the invention, suitable thiophene azo dyesinclude, but are not limited to, the structures shown in Table 5:

Thiophene Azo Dyes No. Formula Example 1 

Example 2 

Example 3 

Example 4 

Example 5 

Example 6 

Example 7 

Example 8 

Example 9 

Example 10

Example 11

Example 12

Example 13

Example 14

Example 15

Example 16

Example 17

Example 18

Example 19

Example 20

Example 21

Example 22

Example 23

Example 24

Example 25

Example 26

Example 27

Example 28

Example 29

Example 30

Example 31

Example 32

Example 33

Example 34

Example 35

Example 36

Example 37

Example 38

Example 39

Example 40

Example 41

Example 42

Laundry Care Compositions

The hueing agents described in the present specification may beincorporated into laundry care compositions including but not limited tolaundry detergents and fabric care compositions. The laundry carecompositions including laundry detergents may be in solid or liquidform, including a gel form, and/or unit does forms, includingmulti-compartment unit dose forms. Such compositions may comprise one ormore of said hueing agents and a laundry care ingredient.

In one aspect, said laundry care composition may comprise, based ontotal laundry care composition weight, less than 15% builder, less than10% builder, or even less than 5% builder. In one aspect, said laundrycare composition may comprise, based on total laundry care compositionweight, a total of no more than 20% water; a total of no more than 15%water; a total of no more than 10% water; or even a total of no morethan 5% water. In one aspect, said laundry care composition maycomprise, rising, based on total laundry care composition weight, fromabout 10% to about 70% of a water-miscible organic solvent having amolecular weight of greater than 70 Daltons.

In one aspect, said laundry care composition may comprise, based ontotal laundry care composition weight, comprising a perfume microcapsulecomprising a core and a shell that encapsulates said core, said perfumemicrocapsule having a D[4,3] average particle of from about 0.01 micronsto about 200 microns and optionally a formaldehyde scavenger that issupplied via the addition of the microcapsules (contained in a perfumemicrocapsule slurry that is added to the laundry care ingredient) and/oradded directly to the laundry care composition. In one aspect, the shellof said perfume microcapsules may be made of any material, includingmaterials selected from the group consisting of polyethylenes,polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters,polyacrylates, polyureas, polyurethanes, polyolefins, polysaccharides,epoxy resins, vinyl polymers, and mixtures thereof. In one aspect,useful shell materials include materials that are sufficientlyimpervious to the core material and the materials in the environment inwhich the perfume microcapsule will be employed, to permit the deliveryperfume to be obtained. Suitable impervious shell materials includematerials selected from the group consisting of reaction products of oneor more amines with one or more aldehydes, such as urea cross-linkedwith formaldehyde or gluteraldehyde, melamine cross-linked withformaldehyde; gelatin-polyphosphate coacervates optionally cross-linkedwith gluteraldehyde; gelatin-gum Arabic coacervates; cross-linkedsilicone fluids; polyamine reacted with polyisocyanates and mixturesthereof. In one aspect, the shell material comprises melaminecross-linked with formaldehyde and/or a polyacrylate. Suitable perfumemicrocapsules may be obtained from Appleton Papers of Appleton Wis.,USA.

In one aspect, suitable formaldehyde scavengers include materialsselected from the group consisting of sodium bisulfite, urea, ethyleneurea, cysteine, cysteamine, lysine, glycine, serine, carnosine,histidine, glutathione, 3,4-diaminobenzoic acid, allantoin, glycouril,anthranilic acid, methyl anthranilate, methyl 4-aminobenzoate, ethylacetoacetate, acetoacetamide, malonamide, ascorbic acid,1,3-dihydroxyacetone dimer, biuret, oxamide, benzoguanamine,pyroglutamic acid, pyrogallol, methyl gallate, ethyl gallate, propylgallate, triethanol amine, succinamide, thiabendazole, benzotriazol,triazole, indoline, sulfanilic acid, oxamide, sorbitol, glucose,cellulose, poly(vinyl alcohol), partially hydrolyzedpoly(vinylformamide), poly(vinyl amine), poly(ethylene imine),poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine),poly(4-aminostyrene), poly(1-lysine), chitosan, hexane diol,ethylenediamine-N,N′-bisacetoacetamide, N-(2-ethylhexyl)acetoacetamide,2-benzoylacetoacetamide, N-(3-phenylpropyl)acetoacetamide, lilial,helional, melonal, triplal, 5,5-dimethyl-1,3-cyclohexanedione,2,4-dimethyl-3-cyclohexenecarboxaldehyde,2,2-dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine,triethylenetetramine, ammonium hydroxide, benzylamine,hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione,dehydroacetic acid, or a mixture thereof. These formaldehyde scavengersmay be obtained from Sigma/Aldrich/Fluka of St. Louis, Mo. U.S.A. orPolySciences, Inc. of Warrington, Pa. U.S.A. Such formaldehydescavengers are typically combined with a slurry containing said perfumemicrocapsules, at a level, based on total slurry weight, of from about 2wt. % to about 18 wt. %, from about 3.5 wt. % to about 14 wt. % or evenfrom about 5 wt. % to about 13 wt. %.

In one aspect, such formaldehyde scavengers may be combined with aproduct containing a perfume microcapsule, said scavengers beingcombined with said product at a level, based on total product weight, offrom about 0.005% to about 0.8%, alternatively from about 0.03% to about0.5%, alternatively from about 0.065% to about 0.25% of the productformulation.

In another aspect, such formaldehyde scavengers may be combined with aslurry containing said perfume microcapsules, at a level, based on totalslurry weight, of from about 2 wt. % to about 14 wt. %, from about 3.5wt. % to about 14 wt. % or even from about 5 wt. % to about 14 wt. % andsaid slurry may be added to a product matrix to which addition anidentical or different scavenger may be added at a level, based on totalproduct weight, of from about 0.005% to about 0.5%, alternatively fromabout 0.01% to about 0.25%, alternatively from about 0.05% to about0.15% of the product formulation.

In one aspect, one or more of the aforementioned formaldehyde scavengersmay be combined with a liquid fabric enhancing product containingperfume microcapsules at a level, based on total liquid fabric enhancingproduct weight, of from 0.005% to about 0.8%, alternatively from about0.03% to about 0.4%, alternatively from about 0.06% to about 0.25% ofthe product formulation.

In one aspect, such formaldehyde scavengers may be combined with aliquid laundry detergent product containing perfume microcapsules, saidscavengers being selected from the group consisting of sodium bisulfite,urea, ethylene urea, cysteine, cysteamine, lysine, glycine, serine,carnosine, histidine, glutathione, 3,4-diaminobenzoic acid, allantoin,glycouril, anthranilic acid, methyl anthranilate, methyl4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide,ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide,benzoguanamine, pyroglutamic acid, pyrogallol, methyl gallate, ethylgallate, propyl gallate, triethanol amine, succinamide, thiabendazole,benzotriazol, triazole, indoline, sulfanilic acid, oxamide, sorbitol,glucose, cellulose, poly(vinyl alcohol), partially hydrolyzedpoly(vinylformamide), poly(vinyl amine), poly(ethylene imine),poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine),poly(4-aminostyrene), poly(l-lysine), chitosan, hexane diol,ethylenediamine-N,N′-bisacetoacetamide, N-(2-ethylhexyl)acetoacetamide,2-benzoylacetoacetamide, N-(3-phenylpropyl)acetoacetamide, lilial,helional, melonal, triplal, 5,5-dimethyl-1,3-cyclohexanedione,2,4-dimethyl-3-cyclohexenecarboxaldehyde,2,2-dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine,triethylenetetramine, ammonium hydroxide, benzylamine,hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione,dehydroacetic acid and mixtures thereof, and combined with said liquidlaundry detergent product at a level, based on total liquid laundrydetergent product weight, of from about 0.003 wt. % to about 0.20 wt. %,from about 0.03 wt. % to about 0.20 wt. % or even from about 0.06 wt. %to about 0.14 wt. %.

The hueing agents may be added to substrates using a variety ofapplication techniques. For instance, for application tocellulose-containing textile substrates, the hueing agent may beincluded as a component of a laundry detergent. Thus, application to acellulose-containing textile substrate actually occurs when a consumeradds laundry detergent to a washing machine. The hueing agent may bepresent in the laundry detergent composition in an amount from about0.000001% to about 10% by weight of the composition, from about 0.00001%to about 10% by weight of the composition, from about 0.0001% to about5% by weight of the composition, and even from about 0.0001% to about 1%by weight of the composition.

The laundry detergent composition typically comprises a surfactant in anamount sufficient to provide desired cleaning properties. In one aspect,the laundry detergent composition may comprise, based on total laundrydetergent composition weight, from about 0.5% to about 99% of thesurfactant; from about 1% to about 95% of the surfactant; from about 5%to about 90% of the surfactant, from about 5% to about 70% of thesurfactant, or even from about 5% to about 40% of the surfactant. Thesurfactant may comprise anionic, nonionic, cationic, zwitterionic and/oramphoteric surfactants. In one aspect, the detergent compositioncomprises anionic surfactant, nonionic surfactant, or mixtures thereof.

Fabric care compositions are typically added in the rinse cycle, whichis after the detergent solution has been used and replaced with therinsing solution in typical laundering processes. The fabric carecompositions disclosed herein may be comprise a rinse added fabricsoftening active and a suitable hueing agent as disclosed in the presentspecification. The fabric care composition may comprise, based on totalfabric care composition weight, from about 1% to about 90%, or fromabout 5% to about 50% fabric softening active. The hueing agent may bepresent in the fabric care composition in an amount from about 0.5 ppbto about 50 ppm, or from about 0.5 ppm to about 30 ppm.

Suitable Laundry Care Ingredients

While not essential for the purposes of the present invention, thenon-limiting list of laundry care ingredients illustrated hereinafterare suitable for use in the laundry care compositions and may bedesirably incorporated in certain aspects of the invention, for exampleto assist or enhance performance, for treatment of the substrate to becleaned, or to modify the aesthetics of the composition as is the casewith perfumes, colorants, dyes or the like. It is understood that suchingredients are in addition to the components that were previouslylisted for any particular aspect. The total amount of such adjuncts mayrange, once the amount of dye is taken into consideration from about 90%to about 99.99999995% by weight of the laundry care composition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable laundry care ingredients include, but are not limited to,fabric softening actives, polymers, for example cationic polymers,surfactants, builders, chelating agents, dye transfer inhibiting agents,dispersants, enzymes, and enzyme stabilizers, catalytic materials,bleach activators, polymeric dispersing agents, clay soilremoval/anti-redeposition agents, brighteners, suds suppressors, dyes,perfume(s) including quadrant perfumes and additional perfume deliverysystems including perfume loaded zeolites, starch encapsuled accords,and Schiff base pro-perfumes, structure elasticizing agents, fabricsofteners, carriers, hydrotropes, processing aids and/or pigments. Inaddition to the disclosure below, suitable examples of such otheradjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282,6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

As stated, the laundry care ingredients are not essential to Applicants'laundry care compositions. Thus, certain aspects of Applicants'compositions do not contain one or more of the following adjunctsmaterials: fabric softening actives, bleach activators, surfactants,builders, chelating agents, dye transfer inhibiting agents, dispersants,enzymes, and enzyme stabilizers, catalytic metal complexes, polymericdispersing agents, clay and soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfumes and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. However, whenone or more adjuncts are present, such one or more adjuncts may bepresent as detailed below:

Surfactants

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C₁₀-C₁₆alkyl benzene sulfonic acids, or C₁₁-C₁₄ alkyl benzene sulfonic acids.In one aspect, the alkyl group is linear and such linear alkyl benzenesulfonates are known as “LAS”. Alkyl benzene sulfonates, andparticularly LAS, are well known in the art. Such surfactants and theirpreparation are described for example in U.S. Pat. Nos. 2,220,099 and2,477,383. Especially useful are the sodium and potassium linearstraight chain alkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about 11 to 14. Sodium C₁₁-C₁₄,e.g., O₁₂, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O)_(n)—SO₃M wherein R′ is a C₈-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In one aspect, R′ isC₁₀-C₁₈ alkyl, n is from about 1 to 15, and M is sodium, potassium,ammonium, alkylammonium, or alkanolammonium. In one aspect, R′ is aC₁₂-C₁₆, n is from about 1 to 6 and M is sodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the compositions of thisinvention and used as or in any anionic surfactant component which maybe present. Specific examples of non-alkoxylated, e.g., non-ethoxylated,alkyl ether sulfate surfactants are those produced by the sulfation ofhigher C₈-C₂₀ fatty alcohols. Conventional primary alkyl sulfatesurfactants have the general formula: ROSO₃-M⁺ wherein R is typically alinear C₈-C₂₀ hydrocarbyl group, which may be straight chain or branchedchain, and M is a water-solubilizing cation. In one aspect, R is aC₁₀-C₁₅ alkyl, and M is alkali metal, more specifically R is C₁₂-C₁₄ andM is sodium.

Specific, non-limiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primary,branched-chain and random alkyl sulfates (AS); c) C₁₀-C₁₈ secondary(2,3) alkyl sulfates having formulae (I) and (II): wherein M in formulae(I) and (II) is hydrogen or a cation which provides charge neutrality,and all M units, whether associated with a surfactant or adjunctingredient, can either be a hydrogen atom or a cation depending upon theform isolated by the artisan or the relative pH of the system whereinthe compound is used, with non-limiting examples of suitable cationsincluding sodium, potassium, ammonium, and mixtures thereof, and x is aninteger of at least about 7, or at least about 9, and y is an integer ofat least 8, or at least about 9; d) C₁₀-C₁₈ alkyl alkoxy sulfates(AE_(x)S) wherein x is from 1-30; e) C₁₀-C₁₈ alkyl alkoxy carboxylatesin one aspect, comprising 1-5 ethoxy units; f) mid-chain branched alkylsulfates as discussed in U.S. Pat. No. 6,020,303 and U.S. Pat. No.6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed inU.S. Pat. No. 6,008,181 and U.S. Pat. No. 6,020,303; h) modifiedalkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242,WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO00/23549, and WO 00/23548; i) methyl ester sulfonate (MES); and j)alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. In one aspect, for use in the liquid detergentproducts herein are those nonionic surfactants which are normallyliquid.

Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.In one aspect, R¹ is an alkyl group, which may be primary or secondary,that comprises from about 9 to 15 carbon atoms, or from about 10 to 14carbon atoms. In one aspect, the alkoxylated fatty alcohols will also beethoxylated materials that contain from about 2 to 12 ethylene oxidemoieties per molecule, or from about 3 to 10 ethylene oxide moieties permolecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17 from about 6 to 15, orfrom about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants havebeen marketed under the tradenames Neodol and Dobanol by the ShellChemical Company.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O. In this formula, Ris a relatively long-chain hydrocarbyl moiety which can be saturated orunsaturated, linear or branched, and can contain from 8 to 20, 10 to 16carbon atoms, or is a C₁₂-C₁₆ primary alkyl. R′ is a short-chain moiety,in one aspect R′ may be selected from hydrogen, methyl and —CH₂OH. Whenx+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy andBO is butyleneoxy. Amine oxide surfactants are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as Pluronic® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x if from 1-30, as discussed in U.S.Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,093,856;f) Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 toLlenado, issued Jan. 26, 1986; specifically alkylpolyglycosides asdiscussed in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; g)Polyhydroxy fatty acid amides as discussed in U.S. Pat. No. 5,332,528,WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ethercapped poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat.No. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactantcomponent may comprise combinations of anionic and nonionic surfactantmaterials. When this is the case, the weight ratio of anionic tononionic will typically range from 10:90 to 90:10, more typically from30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e) aminosurfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708,specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (in one aspect C₁₂ to C₁₈) amine oxides and sulfo and hydroxybetaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate wherethe alkyl group can be C₈ to O₁₈, or O₁₀ to C₁₄.

Non-limiting examples of ampholytic surfactants include aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents comprises at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one comprises an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

Aqueous, Non-Surface Active Liquid Carrier

As noted, the laundry care compositions may be in the form of a solid,either in tablet or particulate form, including, but not limited toparticles, flakes, sheets, or the like, or the compositions may be inthe form of a liquid. The liquid detergent compositions may comprise anaqueous, non-surface active liquid carrier. Generally, the amount of theaqueous, non-surface active liquid carrier employed in the compositionsherein will be effective to solubilize, suspend or disperse thecomposition components. For example, the liquid detergent compositionsmay comprise, based on total liquid detergent composition weight, fromabout 5% to about 90%, from about 10% to about 70%, or from about 20% toabout 70% of the aqueous, non-surface active liquid carrier.

The most cost effective type of aqueous, non-surface active liquidcarrier is typically water. Accordingly, the aqueous, non-surface activeliquid carrier component will generally be mostly, if not completely,comprised of water. While other types of water-miscible liquids, suchalkanols, diols, other polyols, ethers, amines, and the like, have beenconventionally been added to liquid detergent compositions asco-solvents or stabilizers, for purposes of the present invention, theutilization of such water-miscible liquids typically is minimized tohold down composition cost. Accordingly, the aqueous liquid carriercomponent of the liquid detergent products herein will generallycomprise water present in concentrations ranging from about 5% to about90%, or from about 5% to about 70%, by weight of the liquid detergentcomposition.

Bleaching Agents

-   -   Bleaching Agents—The cleaning compositions of the present        invention may comprise one or more bleaching agents. Suitable        bleaching agents other than bleaching catalysts include        photobleaches, bleach activators, hydrogen peroxide, sources of        hydrogen peroxide, pre-formed peracids and mixtures thereof. In        general, when a bleaching agent is used, the compositions of the        present invention may comprise from about 0.1% to about 50% or        even from about 0.1% to about 25% bleaching agent by weight of        the subject cleaning composition. Examples of suitable bleaching        agents include:    -   (1) photobleaches for example sulfonated zinc phthalocyanine;    -   (2) preformed peracids: Suitable preformed peracids include, but        are not limited to, compounds selected from the group consisting        of percarboxylic acids and salts, percarbonic acids and salts,        perimidic acids and salts, peroxymonosulfuric acids and salts,        for example, Oxzone®, and mixtures thereof. Suitable        percarboxylic acids include hydrophobic and hydrophilic peracids        having the formula R—(C═O)O—O-M wherein R is an alkyl group,        optionally branched, having, when the peracid is hydrophobic,        from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and,        when the peracid is hydrophilic, less than 6 carbon atoms or        even less than 4 carbon atoms; and M is a counterion, for        example, sodium, potassium or hydrogen;    -   (3) sources of hydrogen peroxide, for example, inorganic        perhydrate salts, including alkali metal salts such as sodium        salts of perborate (usually mono- or tetra-hydrate),        percarbonate, persulphate, perphosphate, persilicate salts and        mixtures thereof. In one aspect of the invention the inorganic        perhydrate salts are selected from the group consisting of        sodium salts of perborate, percarbonate and mixtures thereof.        When employed, inorganic perhydrate salts are typically present        in amounts of from 0.05 to 40 wt %, or 1 to 30 wt % of the        overall composition and are typically incorporated into such        compositions as a crystalline solid that may be coated. Suitable        coatings include, inorganic salts such as alkali metal silicate,        carbonate or borate salts or mixtures thereof, or organic        materials such as water-soluble or dispersible polymers, waxes,        oils or fatty soaps; and    -   (4) bleach activators having R—(C═O)-L wherein R is an alkyl        group, optionally branched, having, when the bleach activator is        hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon        atoms and, when the bleach activator is hydrophilic, less than 6        carbon atoms or even less than 4 carbon atoms; and L is leaving        group. Examples of suitable leaving groups are benzoic acid and        derivatives thereof—especially benzene sulphonate. Suitable        bleach activators include dodecanoyl oxybenzene sulphonate,        decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or        salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate,        tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene        sulphonate (NOBS). Suitable bleach activators are also disclosed        in WO 98/17767. While any suitable bleach activator may be        employed, in one aspect of the invention the subject cleaning        composition may comprise NOBS, TAED or mixtures thereof.    -   When present, the peracid and/or bleach activator is generally        present in the composition in an amount of from about 0.1 to        about 60 wt %, from about 0.5 to about 40 wt % or even from        about 0.6 to about 10 wt % based on the composition. One or more        hydrophobic peracids or precursors thereof may be used in        combination with one or more hydrophilic peracid or precursor        thereof.    -   The amounts of hydrogen peroxide source and peracid or bleach        activator may be selected such that the molar ratio of available        oxygen (from the peroxide source) to peracid is from 1:1 to        35:1, or even 2:1 to 10:1.    -   Bleach Boosting Compounds—The compositions herein may comprise        one or more bleach boosting compounds. Bleach boosting compounds        provide increased bleaching effectiveness in lower temperature        applications. The bleach boosters act in conjunction with        conventional peroxygen bleaching sources to provide increased        bleaching effectiveness. This is normally accomplished through        in situ formation of an active oxygen transfer agent such as a        dioxirane, an oxaziridine, or an oxaziridinium. Alternatively,        preformed dioxiranes, oxaziridines and oxaziridiniums may be        used.

Among suitable bleach boosting compounds for use in accordance with thepresent invention are cationic imines, zwitterionic imines, anionicimines and/or polyionic imines having a net charge of from about +3 toabout −3, and mixtures thereof. These imine bleach boosting compounds ofthe present invention include those of the general structure:

-   -   where R¹-R⁴ may be a hydrogen or an unsubstituted or substituted        radical selected from the group consisting of phenyl, aryl,        heterocyclic ring, alkyl and cycloalkyl radicals.

Suitable bleach boosting compounds include zwitterionic bleach boosterszwitterionic bleach boosters, which are described in U.S. Pat. Nos.5,576,282 and 5,718,614. Other bleach boosting compounds includecationic bleach boosters described in U.S. Pat. Nos. 5,360,569;5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351,WO 95/13352, and WO 95/13353.

Peroxygen sources are well-known in the art and the peroxygen sourceemployed in the present invention may comprise any of these well knownsources, including peroxygen compounds as well as compounds, which underconsumer use conditions, provide an effective amount of peroxygen insitu. The peroxygen source may include a hydrogen peroxide source, thein situ formation of a peracid anion through the reaction of a hydrogenperoxide source and a bleach activator, preformed peracid compounds ormixtures of suitable peroxygen sources. Of course, one of ordinary skillin the art will recognize that other sources of peroxygen may beemployed without departing from the scope of the invention. The bleachboosting compounds, when present, are typically employed in conjunctionwith a peroxygen source in the bleaching systems of the presentinvention.

-   -   Enzyme Bleaching—Enzymatic systems may be used as bleaching        agents. The hydrogen peroxide may also be present by adding an        enzymatic system (i.e. an enzyme and a substrate therefore)        which is capable of generating hydrogen peroxide at the        beginning or during the washing and/or rinsing process. Such        enzymatic systems are disclosed in EP Patent Application        91202655.6 filed Oct. 9, 1991.

The present invention compositions and methods may utilize alternativebleach systems such as ozone, chlorine dioxide and the like. Bleachingwith ozone may be accomplished by introducing ozone-containing gashaving ozone content from about 20 to about 300 g/m³ into the solutionthat is to contact the fabrics. The gas:liquid ratio in the solutionshould be maintained from about 1:2.5 to about 1:6. U.S. Pat. No.5,346,588 describes a process for the utilization of ozone as analternative to conventional bleach systems and is herein incorporated byreference.

In one aspect, the fabric softening active (“FSA”) is a quaternaryammonium compound suitable for softening fabric in a rinse step. In oneaspect, the FSA is formed from a reaction product of a fatty acid and anaminoalcohol obtaining mixtures of mono-, di-, and, in one aspect,triester compounds. In another aspect, the FSA comprises one or moresoftener quaternary ammonium compounds such, but not limited to, as amonoalkyquaternary ammonium compound, a diamido quaternary compound anda diester quaternary ammonium compound, or a combination thereof.

In one aspect of the invention, the FSA comprises a diester quaternaryammonium (hereinafter “DQA”) compound composition. In certain aspects ofthe present invention, the DQA compounds compositions also encompasses adescription of diamido FSAs and FSAs with mixed amido and ester linkagesas well as the aforementioned diester linkages, all herein referred toas DQA.

A first type of DQA (“DQA (1)”) suitable as a FSA in the present CFSCincludes a compound comprising the formula:

{R_(4-m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)}X⁻

-   -   wherein each R substituent is either hydrogen, a short chain        C₁-C₆, for example C₁-C₃ alkyl or hydroxyalkyl group, e.g.,        methyl, ethyl, propyl, hydroxyethyl, and the like, poly (C₂₋₃        alkoxy), for example. polyethoxy, group, benzyl, or mixtures        thereof; each m is 2 or 3; each n is from 1 to about 4, or 2;        each Y is —O(O)C—, —C(O)—O—, —NR—C(O)—, or —C(O)—NR— and it is        acceptable for each Y to be the same or different; the sum of        carbons in each R¹, plus one when Y is —O—(O)C— or —NR—C(O)—, is        C₁₂-C₂₂, or C₁₄-C₂₀, with each R¹ being a hydrocarbyl, or        substituted hydrocarbyl group; it is acceptable for R¹ to be        unsaturated or saturated and branched or linear and in one        aspect it is linear; it is acceptable for each R¹ to be the same        or different and typically these are the same; and X⁻can be any        softener-compatible anion, suitable anions include, chloride,        bromide, methylsulfate, ethylsulfate, sulfate, phosphate, and        nitrate, in one aspect the anions are chloride or methyl        sulfate. Suitable DQA compounds are typically made by reacting        alkanolamines such as MDEA (methyldiethanolamine) and TEA        (triethanolamine) with fatty acids. Some materials that        typically result from such reactions include        N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or        N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium        methylsulfate wherein the acyl group is derived from animal        fats, unsaturated, and polyunsaturated, fatty acids, e.g.,        tallow, hardended tallow, oleic acid, and/or partially        hydrogenated fatty acids, derived from vegetable oils and/or        partially hydrogenated vegetable oils, such as, canola oil,        safflower oil, peanut oil, sunflower oil, corn oil, soybean oil,        tall oil, rice bran oil, palm oil, etc.

Non-limiting examples of suitable fatty acids are listed in U.S. Pat.No. 5,759,990 at column 4, lines 45-66. In one aspect, the FSA comprisesother actives in addition to DQA (1) or DQA. In yet another aspect, theFSA comprises only DQA (1) or DQA and is free or essentially free of anyother quaternary ammonium compounds or other actives. In yet anotheraspect, the FSA comprises the precursor amine that is used to producethe DQA.

In another aspect of the invention, the FSA comprises a compound,identified as DTTMAC comprising the formula:

[R_(4-m)—N⁽⁺⁾—R¹ _(m)]A⁻

-   -   wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, or C₁₄-C₂₀, but        no more than one being less than about C₁₂ and then the other is        at least about 16, hydrocarbyl, or substituted hydrocarbyl        substituent, for example, C₁₀-C₂₀ alkyl or alkenyl (unsaturated        alkyl, including polyunsaturated alkyl, also referred to        sometimes as “alkylene”), in one aspect C₁₂-C₁₈ alkyl or        alkenyl, and branch or unbranched. In one aspect, the Iodine        Value (IV) of the FSA is from about 1 to 70; each R is H or a        short chain C₁-C₆, or C₁-C₃ alkyl or hydroxyalkyl group, e.g.,        methyl, ethyl, propyl, hydroxyethyl, and the like, benzyl, or        (R²O)₂₋₄H where each R² is a C₁₋₆ alkylene group; and A⁻ is a        softener compatible anion, suitable anions include chloride,        bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or        nitrate; in one aspect the anions are chloride or methyl        sulfate.

Examples of these FSAs include dialkydimethylammonium salts anddialkylenedimethylammonium salts such as ditallowedimethylammonium andditallowedimethylammonium methylsulfate. Examples of commerciallyavailable dialkylenedimethylammonium salts usable in the presentinvention are di-hydrogenated tallow dimethyl ammonium chloride andditallowedimethyl ammonium chloride available from Degussa under thetrade names Adogen® 442 and Adogen® 470 respectively. In one aspect, theFSA comprises other actives in addition to DTTMAC. In yet anotheraspect, the FSA comprises only compounds of the DTTMAC and is free oressentially free of any other quaternary ammonium compounds or otheractives.

In one aspect, the FSA comprises an FSA described in U.S. Pat. Pub. No.2004/0204337 A1, published Oct. 14, 2004 to Corona et al., fromparagraphs 30-79. In another aspect, the FSA is one described in U.S.Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith et al.,on paragraphs 26-31; or U.S. Pat. No. 6,494,920, at column 1, line 51 etseq. detailing an “esterquat” or a quaternized fatty acidtriethanolamine ester salt.

In one aspect, the FSA is chosen from at least one of the following:ditallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methylsulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, orcombinations thereof.

In one aspect, the FSA may also include amide containing compoundcompositions. Examples of diamide comprising compounds may include butnot limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammoniummethyl sulfate (available from Degussa under the trade names Varisoft110 and Varisoft 222). An example of an amide-ester containing compoundisN-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.

Another aspect of the invention provides for a rinse added fabricsoftening composition further comprising a cationic starch. Cationicstarches are disclosed in US 2004/0204337 A1. In one aspect, the rinseadded fabric softening composition comprises from about 0.1% to about 7%of cationic starch by weight of the fabric softening composition. In oneaspect, the cationic starch is HCP401 from National Starch.

-   -   Builders—The compositions of the present invention can comprise        one or more detergent builders or builder systems. When present,        the compositions will typically comprise at least about 1%        builder, or from about 5% or 10% to about 80%, 50%, or even 30%        by weight, of said builder. Builders include, but are not        limited to, the alkali metal, ammonium and alkanolammonium salts        of polyphosphates, alkali metal silicates, alkaline earth and        alkali metal carbonates, aluminosilicate builders        polycarboxylate compounds. ether hydroxypolycarboxylates,        copolymers of maleic anhydride with ethylene or vinyl methyl        ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and        carboxymethyl-oxysuccinic acid, the various alkali metal,        ammonium and substituted ammonium salts of polyacetic acids such        as ethylenediamine tetraacetic acid and nitrilotriacetic acid,        as well as polycarboxylates such as mellitic acid, succinic        acid, oxydisuccinic acid, polymaleic acid, benzene        1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and        soluble salts thereof.    -   Chelating Agents—The compositions herein may also optionally        contain one or more copper, iron and/or manganese chelating        agents. If utilized, chelating agents will generally comprise        from about 0.1% by weight of the compositions herein to about        15%, or even from about 3.0% to about 15% by weight of the        compositions herein.    -   Dye Transfer Inhibiting Agents—The compositions of the present        invention may also include one or more dye transfer inhibiting        agents. Suitable polymeric dye transfer inhibiting agents        include, but are not limited to, polyvinylpyrrolidone polymers,        polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and        N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles        or mixtures thereof. When present in the compositions herein,        the dye transfer inhibiting agents are present at levels from        about 0.0001%, from about 0.01%, from about 0.05% by weight of        the cleaning compositions to about 10%, about 2%, or even about        1% by weight of the cleaning compositions.    -   Dispersants—The compositions of the present invention can also        contain dispersants. Suitable water-soluble organic materials        are the homo- or co-polymeric acids or their salts, in which the        polycarboxylic acid may comprise at least two carboxyl radicals        separated from each other by not more than two carbon atoms.    -   Enzymes—The compositions can comprise one or more detergent        enzymes which provide cleaning performance and/or fabric care        benefits. Examples of suitable enzymes include, but are not        limited to, hemicellulases, peroxidases, proteases, cellulases,        xylanases, lipases, phospholipases, esterases, cutinases,        pectinases, keratanases, reductases, oxidases, phenoloxidases,        lipoxygenases, ligninases, pullulanases, tannases, pentosanases,        malanases, B-glucanases, arabinosidases, hyaluronidase,        chondroitinase, laccase, and amylases, or mixtures thereof. A        typical combination is a cocktail of conventional applicable        enzymes like protease, lipase, cutinase and/or cellulase in        conjunction with amylase.    -   Enzyme Stabilizers—Enzymes for use in compositions, for example,        detergents can be stabilized by various techniques. The enzymes        employed herein can be stabilized by the presence of        water-soluble sources of calcium and/or magnesium ions in the        finished compositions that provide such ions to the enzymes.

Processes of Making Laundry Care Compositions

The laundry care compositions of the present invention can be formulatedinto any suitable form and prepared by any process chosen by theformulator, non-limiting examples of which are described in Applicants'examples and in U.S. Pat. No. 5,879,584; U.S. Pat. No. 5,691,297; U.S.Pat. No. 5,574,005; U.S. Pat. No. 5,569,645; U.S. Pat. No. 5,565,422;U.S. Pat. No. 5,516,448; U.S. Pat. No. 5,489,392; U.S. Pat. No.5,486,303 all of which are incorporated herein by reference.

The liquid detergent compositions may be in the form of an aqueoussolution or uniform dispersion or suspension of surfactant, hueingagent, and certain optional other ingredients, some of which maynormally be in solid form, that have been combined with the normallyliquid components of the composition, such as the liquid alcoholethoxylate nonionic, the aqueous liquid carrier, and any other normallyliquid optional ingredients. Such a solution, dispersion or suspensionwill be acceptably phase stable and will typically have a viscositywhich ranges from about 100 to 600 cps, or from about 150 to 400 cps.For purposes of this invention, viscosity is measured with a BrookfieldLVDV-II+ viscometer apparatus using a #21 spindle.

The liquid detergent compositions herein can be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stableliquid detergent composition. In a process for preparing suchcompositions, a liquid matrix is formed containing at least a majorproportion, or even substantially all, of the liquid components, e.g.,nonionic surfactant, the non-surface active liquid carriers and otheroptional liquid components, with the liquid components being thoroughlyadmixed by imparting shear agitation to this liquid combination. Forexample, rapid stirring with a mechanical stirrer may usefully beemployed. While shear agitation is maintained, substantially all of anyanionic surfactants and the solid form ingredients can be added.Agitation of the mixture is continued, and if necessary, can beincreased at this point to form a solution or a uniform dispersion ofinsoluble solid phase particulates within the liquid phase. After someor all of the solid-form materials have been added to this agitatedmixture, particles of any enzyme material to be included, e.g., enzymeprills, are incorporated. As a variation of the composition preparationprocedure hereinbefore described, one or more of the solid componentsmay be added to the agitated mixture as a solution or slurry ofparticles premixed with a minor portion of one or more of the liquidcomponents. After addition of all of the composition components,agitation of the mixture is continued for a period of time sufficient toform compositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

In one aspect of forming the liquid detergent compositions, the hueingagent is first combined with one or more liquid components to form ahueing agent premix, and this hueing agent premix is added to acomposition formulation containing a substantial portion, for examplemore than 50% by weight, more specifically, more than 70% by weight, andyet more specifically, more than 90% by weight, of the balance ofcomponents of the laundry detergent composition. For example, in themethodology described above, both the hueing agent premix and the enzymecomponent are added at a final stage of component additions. In anotheraspect, the hueing agent is encapsulated prior to addition to thedetergent composition, the encapsulated hueing agent is suspended in astructured liquid, and the suspension is added to a compositionformulation containing a substantial portion of the balance ofcomponents of the laundry detergent composition.

As noted previously, the detergent compositions may be in a solid form.Suitable solid forms include tablets and particulate forms, for example,granular particles, flakes or sheets. Various techniques for formingdetergent compositions in such solid forms are well known in the art andmay be used herein. In one aspect, for example when the composition isin the form of a granular particle, the hueing agent is provided inparticulate form, optionally including additional but not all componentsof the laundry detergent composition. The hueing agent particulate iscombined with one or more additional particulates containing a balanceof components of the laundry detergent composition. Further, the hueingagent, optionally including additional but not all components of thelaundry detergent composition, may be provided in an encapsulated form,and the hueing agent encapsulate is combined with particulatescontaining a substantial balance of components of the laundry detergentcomposition.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingof fabrics. Generally, an effective amount of such compositions is addedto water, for example in a conventional fabric laundering automaticwashing machine, to form such aqueous laundering solutions. The aqueouswashing solution so formed is then contacted, typically under agitation,with the fabrics to be laundered therewith. An effective amount of theliquid detergent compositions herein added to water to form aqueouslaundering solutions can comprise amounts sufficient to form from about500 to 7,000 ppm of composition in aqueous washing solution, or fromabout 1,000 to 3,000 ppm of the detergent compositions herein will beprovided in aqueous washing solution.

Method of Use

Certain of the consumer products disclosed herein can be used to cleanor treat a situs inter alia a surface or fabric. Typically at least aportion of the situs is contacted with an embodiment of Applicants'consumer product, in neat form or diluted in a liquor, for example, awash liquor and then the situs may be optionally washed and/or rinsed.In one aspect, a situs is optionally washed and/or rinsed, contactedwith an aspect of the consumer product and then optionally washed and/orrinsed. For purposes of the present invention, washing includes but isnot limited to, scrubbing, and mechanical agitation. The fabric maycomprise most any fabric capable of being laundered or treated in normalconsumer use conditions. Liquors that may comprise the disclosedcompositions may have a pH of from about 3 to about 11.5. Suchcompositions are typically employed at concentrations of from about 500ppm to about 15,000 ppm in solution. When the wash solvent is water, thewater temperature typically ranges from about 5° C. to about 90° C. and,when the situs comprises a fabric, the water to fabric ratio istypically from about 1:1 to about 30:1. Employing one or more of theaforementioned methods results in a treated situs.

In one aspect, a method of treating and/or cleaning a surface or fabriccomprising the steps of optionally washing and/or rinsing said surfaceor fabric, contacting said surface or fabric with any laundry carecomposition disclosed in this specification, then optionally washingand/or rinsing said surface and/or fabric then optionally letting saidsurface or fabric to dry and/or actively drying said surface or fabric,is disclosed.

EXAMPLES

The following examples are provided to further illustrate the hueingagents of the present invention; however, they are not to be construedas limiting the invention as defined in the claims appended hereto. Infact, it will be apparent to those skilled in the art that variousmodifications and variations can be made in this invention withoutdeparting from the scope or spirit of the invention. All parts andpercents given in these examples are by weight unless otherwiseindicated.

Sample Preparation and Test Methods A. Sample Preparation

The following general procedures were used to prepare the thiophene azodyes of the present invention.

Preparation of Glycidol Materials

18 parts N-ethyl-m-toluidine, 52 parts isopropyl-glycidyl ether, and 50parts toluene were charged into a 200 mL round bottom flask at roomtemperature. The mixture was refluxed overnight. The solvent was removedand the resulting material was used crude for the next step. Thesematerials were then alkoxylated as described herein.

Preparation of Alkoxylated Intermediates General Procedure forAlkoxylation—Method A:

Intermediate Type 1, initial single site polymer

18 parts N-ethyl-m-toluidine, 14 parts acetic acid, and 20 parts waterwere charged into a 200 mL stainless steel autoclave at roomtemperature. 11 parts ethylene oxide was added over several hours. Afterthe reaction was kept for 24 hours at room temperature, the vessel wascharged with 0.2 parts NaOH and heated up to 125° C. Then, ethyleneoxide was added over about 1 hour. After continuing the reaction foranother 3 hours at 125° C., residual EO was removed by vacuum. Then itwas cooled to room temperature and the intermediate obtained was anamber-colored viscous liquid. The constant average number of EO could beachieved every time by controlling the amount of ethylene oxide in thesynthesis.

Intermediate Type 2, Initial Dual Chain Polymer

18 parts 2-Methoxy-5-methylaniline, 14 parts acetic acid, and 20 partswater were charged into a 200 mL stainless steel autoclave at roomtemperature. 22 parts ethylene oxide was added over several hours. Afterthe reaction was kept for 24 hours at room temperature, the vessel wascharged with 0.2 parts NaOH and heated up to 125° C. Then, 40 partsethylene oxide was added over about 1 hour. After continuing thereaction for another 3 hours at 125° C., residual EO was removed byvacuum. Then it was cooled to room temperature and the intermediateobtained was an amber-colored viscous liquid. The constant averagenumber of EO could be achieved every time by controlling the amount ofethylene oxide in the synthesis.

General Procedure for Alkoxylation—Method B:

18 parts aniline, 60 parts mono-bromo-polyethylene glycol-200, 20 partsNaHCO₃ and 50 parts toluene were charged into a 200 mL round bottomflask at room temperature. The reaction mixture was heated to 80° C. for5 hours. The salt was filtered and the solvent removed from the filtratevia low pressure distillation. The crude product was used with nofurther purification for the next step.

It is also possible to use a mono-bromo-mono-chloro glycol in order todirectly make the halogenated product using this same procedure above.

General Procedure for Tosylation of Intermediates

Intermediate Type 1

To a mixture of 44 parts N-ethyl —N-alkylene oxide-m-toluidine and 41parts tosyl chloride in 20 parts water was slowly added 20 parts 25%NaOH. The reaction mixture was then allowed to stir for 4 hours at roomtemperature. The mixture was diluted with 400 parts water and thenneutralized by addition of 33% hydrochloric acid. 400 parts ethylacetate was added and the mixture was phase separated. The organic phasewas dried over anhydrous sodium sulfate, filtered and the solventevaporated. The crude product was immediately used for the next step.

Intermediate Type 2

To a mixture of 44 parts 2-methoxy-5-methyl-N-bis-alkyleneoxide-anilineand 82 parts tosyl chloride in 30 parts water was slowly added 30 parts25% NaOH. The reaction mixture was then allowed to stir for 4 hours atroom temperature. The mixture was diluted with 400 parts water and thenneutralized by addition of 33% hydrochloric acid. 400 parts ethylacetate was added and the mixture was phase separated. The organic phasewas dried over anhydrous sodium sulfate, filtered and the solventevaporated. The crude product was immediately used for the next step.

General Procedure for Quaternization

Intermediate Type 1

40 parts of the tosylated intermediate, 20 parts dimethylaminopropylsulfonate and 100 parts chloroform were mixed and refluxed for 6 hours.The material was then cooled down and 200 parts water was added. Thematerial was phase separated and the aqueous phase was found to containthe desired product. The aqueous phase was dried down via low pressuredistillation. The chloride material can be used in the same way to makethe chloro salt version.

Intermediate Type 2

40 parts of the tosylated intermediate, 30 parts triethylamine and 100parts chloroform were mixed and refluxed for 6 hours. The material wasthen cooled down and 200 parts water was added. The material was phaseseparated and the aqueous phase was found to contain the desiredproduct. The aqueous phase was dried down via low pressure distillation

General Procedures for Color Synthesis

All colors were prepared following the same general procedure.

Example 12

2 parts amino-thiophene, and 30 parts phosphoric acid, were charged into200 mL glass flask and cooled to 0-5° C. 1 part NaNO₂ was slowly addedas a solid, maintaining the temperature below 10° C. When addition wascompleted for diazotization, the mixture was stirred for 30 minutes andexcess sodium nitrite was consumed by adding 0.3 parts sulfamic acid.Enough sulfamic acid was added until starch iodide paper provided anegative result. To a separate flask was added the 6 parts of thequaternized material prepared following Intermediate Type 1 route,wherein quaternization was done using 1 molar equivalent oftriethylamine and 12 parts water. The prepared diazonium salt solutionwas slowly added into the above solution for coupling reaction. Care wastaken to not allow the temperature to rise above 10° C. After completeaddition of diazonium salt solution, the reaction was allowed to slowlyreach room temperature over an hour. The mixture was then neutralizedwith sodium hydroxide and phase separated. The product layer was thendissolved with methanol and filtered to remove any excess salts. Thefiltrate was evaporated and the product of this reaction can be used atthis point or further diluted with water to a lower viscosity.

Example 1

Example 1 was prepared via the Intermediate Type 2 procedures, whereinonly 2 moles of ethylene oxide were added to the initial material andthe tosylated material was quaternized by using 2 molar equivalentsN-methyl imidazole. Colorant synthesis was as described in Example 12.

Example 2

Example 2 was prepared as Example 1, except the initial alkoxylation wasdone using m-toluidine.

Example 7

Example 7 was prepared via the Intermediate Type 1 procedures, whereinonly 1 mole of ethylene oxide was added to the N-ethyl-aniline and thetosylated material was quaternized by using 1 molar equivalenttriethylamine. Colorant synthesis was as described in Example 12.

Example 13

Example 13 was prepared as Example 12, except quaternization was donewith N-methyl imidazole.

Example 14

Example 14 was prepared as Example 12, except quaternization was donewith N,N-Dimethyl-glycine.

Example 15

Example 15 was prepared as Example 12, except quaternization was donewith N,N-Dimethylpropyl sulfonate.

Example 18

Example 18 was prepared via the Intermediate Type 2 procedures andcolorant synthesis was as described in Example 12.

Example 19

Example 19 was prepared via the Intermediate Type 2 procedures, whereinthe initial alkoxylation was done using 2,5-dimethoxyaniline andcolorant synthesis was as described in Example 12.

Example 21

Example 21 was prepared via the Intermediate Type 2 procedures, whereinquaternization was done using dimethylethanolamine and colorantsynthesis was as described in Example 12.

Example 22

Example 22 was prepared via the Intermediate Type 2 procedures, whereinquaternization was done using triethanolamine and colorant synthesis wasas described in Example 12.

Example 35

Example 35 was prepared via the Intermediate Type 2 procedures, whereinalkoxylation was done using m-toluidine and quaterinzation was doneusing triethylamine. Colorant synthesis was as described in Example 12.

Example 36

Example 36 was prepared as Example 1, except that the initialalkoxylation was done using m-toluidine and quaternization was doneusing triethylamine. Color synthesis was as described in Example 12.

B. Test Methods I. Method for Determining the Aqueous Partition Value ofa Dye

Dissolve in deionized water to a final volume of 10.0 mL an amount ofdye sufficient to provide a solution absorbance value between 0.25 and1.0, said absorbance being determined at the dye λ_(max) between 400 nmand 750 nm, using a cuvette with 1.0 cm path length. Measure theabsorbance of the sample at the dye λ_(max) in a UV/Visspectrophotometer, then transfer the entire 10.0 mL solution to a 50.0mL plastic centrifuge tube. Add 10.0 mL of 1-octanol, cap the tube, andmix vigorously for 30 seconds using a Vortex™ mixer. Leave the tubestanding undisturbed until the layers cleanly phase separate. If thelayers do not cleanly separate within several hours, centrifuge toobtain phase separation.

Using a transfer pipette, withdraw an aliquot of the aqueous (bottom)layer and transfer it to a cuvette with 1.0 cm path length forspectrophotometric analysis. Analyze the solution as before, andquantify the absorbance loss at λ_(max) as “% of Dye Remaining inAqueous Layer” as detailed below:

% of Dye Remaining in Aqueous Layer=Aqueous Partition Value(APV)=(A_(f)/A_(i))×100%

wherein A_(i) is the initial solution absorbance at λ_(max) and A_(f) isthe final solution absorbance at λ_(max).

II. Method for Determining Hueing Efficiency for Detergents

-   -   a.) Two 25 cm×25 cm fabric swatches of 16 oz white cotton        interlock knit fabric (270 g/square meter, brightened with        Uvitex BNB fluorescent whitening agent, from Test Fabrics. P.O.        Box 26, Weston, Pa., 18643) are obtained.    -   b.) Prepare two one liter aliquots of tap water containing 1.55        g of AATCC standard heavy duty liquid (HDL) test detergent.    -   c.) Add a sufficient amount the dye to be tested to one of the        aliquots from Step b.) above to produce an aqueous solution        absorbance of 1 AU.    -   d.) Wash one swatch from a.) above in one of the aliquots of        water containing 1.55 g of AATCC standard heavy duty liquid        (HDL) test detergent and wash the other swatch in the other        aliquot. Such washing step should be conducted for 30 minutes at        room temperature with agitation. After such washing step        separately rinse the swatches in tap water and air dry the        swatches in the dark.    -   e.) After rinsing and drying each swatch, the hueing efficiency,        DE*_(eff), of the dye is assessed by determining the L*, a*, and        b* value measurements of each swatch using a Hunter LabScan XE        reflectance spectrophotometer with D65 illumination, 10°        observer and UV filter excluded. The hueing efficiency of the        dye is then calculated using the following equation:

DE* _(eff)=((L* _(c) −L _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²)^(1/2)

-   -   -   wherein the subscripts c and s respectively refer to the L*,            a*, and b* values measured for the control, i.e., the fabric            sample washed in detergent with no dye, and the fabric            sample washed in detergent containing the dye to be            screened.

III. Method for Determining Wash Removability

-   -   a.) Prepare two separate 150 ml aliquots of HDL detergent        solution, according to AATCC Test Method 61-2003, Test 2A and        containing 1.55 g/liter of the AATCC HDL formula in distilled        water.    -   b.) A 15 cm×5 cm sample of each fabric swatch from the Method        for Determining of Hueing Efficiency For Detergents described        above is washed in a Launderometer for 45 minutes at 49° C. in        150 ml of a the HDL detergent solution prepared according to        Step 11. a.) above.    -   c.) The samples are rinsed with separate aliquots of rinse water        and air dried in the dark, and then L*, a*, and b* value        measurements of each swatch are taken using a Hunter LabScan XE        reflectance spectrophotometer with D65 illumination, 10°        observer and UV filter excluded. The amount of residual        coloration is assessed by measuring the DE*_(res), calculated        using the following equation:

DE* _(res)=((L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²)^(1/2)

-   -   -   wherein the subscripts c and s respectively refer to the L*,            a*, and b* values measured for the control, i.e., the fabric            sample initially washed in detergent with no dye, and the            fabric sample initially washed in detergent containing the            dye to be screened. The wash removal value for the dye is            then calculated according to the formula: %            removal=100×(1−DE*_(res)/DE*_(eff))

C. Test Results

The aqueous partitioning values of several examples are provided inTable 6.

TABLE 6 Aqueous Partitioning Values of Thiophene Azo Dyes % Dye in % Dyein Octanol Layer Dye Water Layer (Presumed) Example 1 97%  3% Example 283% 17% Example 7 15% 85% Example 12 15% 85% Example 13 20% 80% Example14  4% 96% Example 15  3% 97% Example 18 49% 51% Example 19 78% 22%Example 21 75% 25% Example 22 56% 44% Example 35 66% 34% Example 36 94% 6%

Exemplary Detergent Formulations Formulations 1a-11: Liquid DetergentFormulations

Tables 7A and 7B provide examples of liquid detergent formulations whichinclude at least one thiophene azo dye of the present invention as ahueing agent. The formulations are shown in Table 7A as Formulations 1athrough 1f and in Table 7B as Formulations 1g through 1l.

TABLE 7A Liquid Detergent Formulations Comprising the Inventive HueingAgent 1a 1b 1c 1d 1e 1f⁵ Ingredient wt % wt % wt % wt % wt % wt % sodiumalkyl ether sulfate 14.4% 14.4% 9.2% 5.4% linear alkylbenzene sulfonicacid 4.4% 4.4% 12.2% 5.7% 1.3% 22.0% alkyl ethoxylate 2.2% 2.2% 8.8%8.1% 3.4% 18.0% amine oxide 0.7% 0.7% 1.5% citric acid 2.0% 2.0% 3.4%1.9% 1.0% 1.6% fatty acid 3.0% 3.0% 8.3% 16.0% protease 1.0% 1.0% 0.7%1.0% 2.5% amylase 0.2% 0.2% 0.2% 0.3% lipase 0.2% borax 1.5% 1.5% 2.4%2.9% calcium and sodium formate 0.2% 0.2% formic acid 1.1% amineethoxylate polymers 1.8% 1.8% 2.1% 3.2% sodium polyacrylate 0.2% sodiumpolyacrylate copolymer 0.6% DTPA¹ 0.1% 0.1% 0.9% DTPMP² 0.3% EDTA³ 0.1%fluorescent whitening agent 0.15% 0.15% 0.2% 0.12% 0.12% 0.2% ethanol2.5% 2.5% 1.4% 1.5% propanediol 6.6% 6.6% 4.9% 4.0% 15.7% sorbitol 4.0%ethanolamine 1.5% 1.5% 0.8% 0.1% 11.0% sodium hydroxide 3.0% 3.0% 4.9%1.9% 1.0% sodium cumene sulfonate 2.0% silicone suds suppressor 0.01%perfume 0.3% 0.3% 0.7% 0.3% 0.4% 0.6% Non-tinting dyes⁴ 0.0001% 0.001%0.008% 0.03% 0.015% 0.05% Hueing Agent⁶ 0.01% 0.005% Hueing Agent⁷ 0.01%0.02% 0.003% 0.012% water balance balance balance balance balancebalance 100.0% 100.0% 100.0% 100.0% 100.0% 100.0%

TABLE 7B Liquid Detergent Formulations Comprising the Inventive HueingAgent 1g 1h 1i 1j 1k 1l⁵ Ingredient wt % wt % wt % wt % wt % wt % sodiumalkyl ether sulfate 14.4% 14.4% 9.2% 5.4% linear 1benzene sulfonic acid4.4% 4.4% 12.2% 5.7% 1.3% 22.0% alkyl ethoxylate 2.2% 2.2% 8.8% 8.1%3.4% 18.0% amine oxide 0.7% 0.7% 1.5% citric acid 2.0% 2.0% 3.4% 1.9%1.0% 1.6% fatty acid 3.0% 3.0% 8.3% 16.0% protease 1.0% 1.0% 0.7% 1.0%1.7% amylase 0.2% 0.2% 0.2% 0.6% lipase 0.2% 0.2% borax 1.5% 1.5% 2.4%2.9% calcium and sodium formate 0.2% 0.2% formic acid 1.1% amineethoxylate polymers 1.8% 1.8% 2.1% 3.2% sodium polyacrylate 0.2% sodiumpolyacrylate copolymer 0.6% DTPA¹ 0.1% 0.1% 0.9% DTPMP² 0.3% EDTA³ 0.1%fluorescent whitening agent 0.15% 0.15% 0.2% 0.12% 0.12% 0.2% ethanol2.5% 2.5% 1.4% 1.5% propanediol 6.6% 6.6% 4.9% 4.0% 15.7% sorbitol 4.0%ethanolamine 1.5% 1.5% 0.8% 0.1% 11.0% sodium hydroxide 3.0% 3.0% 4.9%1.9% 1.0% sodium cumene sulfonate 2.0% silicone suds suppressor 0.01%perfume 0.3% 0.3% 0.7% 0.3% 0.4% 0.6% Non-tinting dyes⁴ 0.0001% 0.001%0.008% 0.03% 0.015% 0.05% Hueing Agent⁶ 0.01% 0.005% Hueing Agent⁷ 0.01%0.02% 0.003% 0.012% opacifier⁸ 0.5% water balance balance balancebalance balance balance 100.0% 100.0% 100.0% 100.0% 100.0% 100.0%Footnotes for Formulations 1a-l: ¹diethylenetriaminepentaacetic acid,sodium salt ²diethylenetriaminepentakismethylenephosphonic acid, sodiumsalt ³ethylenediaminetetraacetic acid, sodium salt ⁴a non-tinting dyesused to adjust formula color ⁵compact formula, packaged as a unitizeddose in polyvinyl alcohol film ⁶thiophene azo hueing agent from Table 5,Examples 1-21, preferably with hueing efficiency >10 and washremovability 30-85% ⁷thiophene azo hueing agent from Table 5, Examples22-42, preferably with hueing efficiency >10 and wash removability30-85% ⁸Acusol OP301

Formulations 2a-2e: Granular Detergent Formulations

Table 8 provides examples of granular detergent formulations whichinclude at least one thiophene azo dye of the present invention as ahueing agent. The formulations are shown in Table 8 as Formulations 2athrough 2e.

TABLE 8 Granular Detergent Formulations Comprising the Inventive HueingAgent 2a 2b 2c 2d 2e Ingredient wt % wt % wt % wt % wt % Na linearalkylbenzene sulfonate 3.4% 3.3% 11.0% 3.4% 3.3% Na alkylsulfate 4.0%4.1% 4.0% 4.1% Na alkyl sulfate (branched) 9.4% 9.6% 9.4% 9.6% alkylethoxylate 3.5% type A zeolite 37.4% 35.4% 26.8% 37.4% 35.4% sodiumcarbonate 22.3% 22.5% 35.9% 22.3% 22.5% sodium sulfate 1.0% 18.8% 1.0%sodium silicate 2.2% protease 0.1% 0.2% 0.1% 0.2% sodium polyacrylate1.0% 1.2% 0.7% 1.0% 1.2% carboxymethylcellulose 0.1% PEG 600 0.5% 0.5%PEG 4000 2.2% 2.2% DTPA 0.7% 0.6% 0.7% 0.6% fluorescent whitening agent0.1% 0.1% 0.1% 0.1% 0.1% sodium percarbonate 5.0% 5.0% sodiumnonanoyloxybenzenesulfonate 5.3% 5.3% silicone suds suppressor 0.02%0.02% 0.02% 0.02% perfume 0.3% 0.3% 0.2% 0.3% 0.3% Hueing Agent ¹ 0.004%0.02% Hueing Agent ² 0.006% 0.002% 0.004% water and miscellaneousbalance balance balance balance balance 100.0% 100.0% 100.0% 100.0%100.0% Footnotes for Formulations 2a-e: ¹ thiophene azo hueing agentfrom Table 5, Examples 1-21, preferably with hueing efficiency >10 andwash removability 30-85% ² thiophene azo hueing agent from Table 5,Examples 22-42, preferably with hueing efficiency >10 and washremovability 30-85%

Exemplary Fabric Care Compositions Formulations 3a-3d: Liquid FabricCare Compositions

Table 9 provides examples of liquid fabric care compositions whichinclude at least one thiophene azo dye of the present invention as ahueing agent. The compositions are shown in Table 9 as Formulations 3athrough 3d.

TABLE 9 Liquid Fabric Care Compositions Comprising the Inventive HueingAgent Ingredients 3a 3b 3c 3d Fabric Softening 13.70% 13.70% 13.70%13.70% Active ^(a) Ethanol 2.14% 2.14% 2.14% 2.14% Cationic Starch ^(b)2.17% 2.17% 2.17% 2.17% Perfume 1.45% 1.45% 1.45% 1.45% PhaseStabilizing 0.21% 0.21% 0.21% 0.21% Polymer ^(c) Calcium Chloride 0.147%0.147% 0.147% 0.147% DTPA ^(d) 0.007% 0.007% 0.007% 0.007% Preservative^(e)  5 ppm  5 ppm  5 ppm  5 ppm Antifoam ^(f) 0.015% 0.015% 0.015%0.015% Hueing Agent. ^(g) 30 ppm 15 ppm Hueing Agent ^(h) 30 ppm HueingAgent ^(i) 30 ppm 15 ppm Tinopal CBS-X ^(j) 0.2 0.2 0.2 0.2 EthoquadC/25 ^(k) 0.26 0.26 0.26 0.26 Ammonium Chloride 0.1% 0.1% 0.1% 0.1%Hydrochloric Acid 0.012% 0.012% 0.012% 0.012% Deionized Water BalanceBalance Balance Balance Footnotes for Formulations 3a-d: ^(a)N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride. ^(b) Cationicstarch based on common maize starch or potato starch, containing 25% to95% amylose and a degree of substitution of from 0.02 to 0.09, andhaving a viscosity measured as Water Fluidity having a value from 50 to84. ^(c) Copolymer of ethylene oxide and terephthalate having theformula described in U.S. Pat. No. 5,574,179 at col. 15, lines 1-5,wherein each X is methyl, each n is 40, u is 4, each R¹ is essentially1,4-phenylene moieties, each R² is essentially ethylene, 1,2-propylenemoieties, or mixtures thereof. ^(d) Diethylenetriaminepentaacetic acid.^(e) KATHON ® CG available from Rohm and Haas Co. ^(f) Silicone antifoamagent available from Dow Corning Corp. under the trade name DC2310. ^(g)thiophene azo hueing agent from Table 5, Examples 1-21, preferably withhueing efficiency >10 and wash removability 30-85% ^(h) thiophene azohueing agent from Table 5, Examples 22-42, preferably with hueingefficiency >10 and wash removability 30-85% ^(i) thiophene azo hueingagent from Table 5, Examples 1-42, preferably with hueing efficiency >10and wash removability 30-85% ^(j) Disodium 4,4′-bis-(2-sulfostyryl)biphenyl, available from Ciba Specialty Chemicals. ^(k) Cocomethylethoxylated [15] ammonium chloride, available from Akzo Nobel.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular aspects of the present invention have been illustratedand described, it would be obvious to those skilled in the art thatvarious other changes and modifications can be made without departingfrom the spirit and scope of the invention. It is therefore intended tocover in the appended claims all such changes and modifications that arewithin the scope of this invention.

1. A thiophene azo dye containing a formally charged moiety, with theproviso that the dye does not comprise ameta-bis(2-hydroxy-3-trimethylammoniumpropyl)amino tolyl group.
 2. Thethiophene azo dye of claim 1, said dye having, in the wavelength rangeof about 400 nm to about 750 nm in methanol solution, a maximumextinction coefficient from about 1000 to about 1,000,000 liter/mol/cm.3. The thiophene azo dye of claim 2, said dye having, in the wavelengthrange of about 560 nm to about 610 nm, a maximum extinction coefficientfrom about 20,000 to about 250,000 liter/mol/cm.
 4. The thiophene azodye of claim 1, said dye having a molecular weight from greater than 300daltons.
 5. The thiophene azo dye of claim 1, said dye having an aqueouspartition value from about 10% to 100%, said dye comprising anon-covalently bound charge balancing counterion.
 6. The thiophene azodye of claim 1, said dye having an aqueous partition value from 0% toabout 40%, said dye comprising a covalently bound charge balancingcounterion.
 7. The thiophene azo dye of claim 1, wherein said dye isrepresented by general Formula (I):

wherein: a.) R₁, R₂ and R₃ are each independently selected fromhydrogen, electron-withdrawing moieties, and electron-donating moieties,provided that at least one of R₁, R₂ and R₃ is an electron-withdrawingmoiety; and b.) wherein X is an organic moiety having a molecular weightfrom about 65 daltons to about 4855 daltons.
 8. The thiophene azo dye ofclaim 7, wherein each R₁, R₂ and R₃ is independently selected fromhydrogen, (C₁-C₄)-alkyl, (C₃-C₁₀)-aryl, carboxylate, cyano, sulfonate,phosphonate, sulfate, acetate, nitro, (C₁-C₄)-alkyl ester, halogen oramino moiety.
 9. The thiophene azo dye of claim 7, wherein X is a moietyhaving Formula (II) below:

wherein: i.) R₄ is selected from a moiety having Formula (III) below

wherein: i.) Each R₈ is independently selected from hydrogen, C₁-C₈alkyl optionally substituted with a hydroxy, or acetyl; ii.) m is aninteger from 0 to 10; iii.) Y is selected from a sulfonate, carboxylate,a phosphonate or quaternary ammonium species selected from animidazolium, pyridinium, morpholinium, piperidinium, or a moiety havingFormula (IV) below:

wherein: i.) R₉ is a C₁-C₈ alkyl moiety optionally substituted with —OH,ii.) R₁₀ is selected from C₁-C₁₈ alkyl moiety optionally substitutedwith —OH, or C₂-C₈ alkyl substituted with sulfonate, or C₁-C₈ alkylsubstituted with carboxylate, iii.) Z is a charge balancing counterionof unit charge c; the index b is 1 when R₁₀ is a C₁-C₁₈ alkyl moietyoptionally substituted with —OH, otherwise the index b=0; Or, R₄ isselected from a moiety having Formula (V) below:

wherein i.) Each R₁₁ and R₁₂ is independently selected from hydrogen,C₁-C₈ alkyl, aryl, acetyl or hydroxyl moiety; m and n are independentand are integers from 0 to 10, ii.) Y is as described above; Or, R₄ isselected from a moiety having Formula (VI) below:

wherein i.) R₁₃ is selected from an aryl moiety, arylalkyl moiety,C₁-C₁₈ alkyl moiety, or a siloxane moiety; ii.) Each R₁₄ isindependently selected from hydrogen, C₁-C₄ alkyl; m is an integer from0 to 10; iii.) Y is as described above; ii.) R₅ can be the same as R₄ orselected from C₁-C₁₂ alkyl moiety, aryl moiety or arylalkyl moiety;wherein the index (a) is an integer from 0 to 4, and each R₆ may beindependently selected from a C₁-C₆ alkyl, a C₁-C₄ alkoxy, a nitro, ahydroxyl, a halogen, or —NHC(O)R₂₂ wherein R₂₂ is selected from H, —NH₂,C₁-C₆ alkyl, phenyl, —(CH₂)_(s)OR₂₃ where the index s is 1 or 2 and R₂₃is selected from Me, phenyl, and —CO₂CH₂CN; —NHSO₂R₂₄ wherein R₂₄ isC₁-C₄ alkyl or phenyl; said alkyl, alkoxy and acetamido moieties may beoptionally substituted with a formally charged moiety; Or, X is a moietyhaving Formula VII below:

wherein each R₄ and R₅ can independently be selected from: a)[(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)R₁₅]; b) alkyl, aryl or aryl alkyl; c)[CH₂CH(OR₁₆)CH₂OR₁₇]; d) the amino addition product of styrene oxide,glycidyl methyl ether, isobutyl glycidyl ether, isopropylglycidyl ether,t-butyl glycidyl ether, 2-ethylhexylgycidyl ether, and glycidylhexadecylether, followed by the addition of from 1 to 10 alkylene oxide unitswherein at least one such alkyleneoxide unit is substituted with R₁₅that is not —H; wherein R′ is selected from the group consisting of H,CH₃, CH₂—O—(CH₂CH₂O)_(z)1R₁₅, and mixtures thereof; R″ is selected fromthe group consisting of H, CH₂—O(CH₂CH₂O)_(z)R₁₅, and mixtures thereof;x+y≦20; y≧1; z=0 to 10; each R₁₅ is independently selected from —H and—CH₂CHR₁₈N⁺R₁₉R₂₀R₂₁ wherein R₁₈ is selected from —H and —CH₃; each R₁₉and R₂₀ is independently selected from C₁-C₄ alkyl optionallysubstituted with —OH; R₂₁ is independently selected from C₁-C₁₂optionally —OH substituted alkyl or (CH₂)_(r)O_(p)Q; the index r is aninteger from 1 to 8; the index p is 0 or 1; and wherein Q is an anionicgroup selected from —CO₂ ⁻, and —SO₃ ⁻; R₁₆ is selected from the groupconsisting of H, (CH₂CH₂O)_(z)R₁₅ wherein z=0 to 10, and mixturesthereof; R₁₇ is selected from the group consisting of C₁-C₁₆ alkyl,C₆-C₁₀ aryl groups, and mixtures thereof; the index m is an integer from0 to 4 and each R₆ is as defined above; Z is a charge balancingcounterion of unit charge c; the index b is equal to the number of non-HR₁₅ groups that do not comprise a covalently bound charge balancingcounterion; further provided the molecule contains at least one non-HR₁₅ group.
 10. The thiophene azo dye of claim 9, wherein X is a moietyhaving Formula (II) below:

wherein: i.) R₄ is selected from a moiety having Formula (III) below

wherein: i.) R₈ is a hydrogen, C₁-C₄ alkyl moiety or aryl moiety; ii.) Yis a quaternary ammonium species selected from a group consisting of animidazolium, or a moiety having Formula (IV) below:

wherein: i.) R₉ is a C₁-C₂ alkyl moiety, ii.) R₁₀ is selected from C₁-C₈alkyl moiety optionally substituted with —OH, or C₂-C₄ alkyl substitutedwith sulfonate, or C₁-C₄ alkyl substituted with carboxylate, iii.) Z isa charge balancing counterion of unit charge c; the index b is 1 whenR₁₀ is a C₁-C₈ alkyl moiety optionally substituted with —OH, otherwisethe index b=0; Or, R₄ is selected from a moiety having Formula (V)below:

wherein i.) Each R₁₁ and R₁₂ is independently selected from hydrogen,C₁-C₄ alkyl or aryl moiety; m and n are independent and are integersfrom 0 to 5, ii.) Y is as described above; Or, R₄ is selected from amoiety having Formula (VI) below:

wherein i.) R₁₃ is selected from an aryl moiety, benzyl moiety, or aC₁-C₁₈ alkyl moiety; ii.) Each R₁₄ is independently selected fromhydrogen or —CH₃; m is an integer from 0 to 10, ii.) R₅ can be the sameas R₄ or selected from C₁-C₆ alkyl moiety or benzyl moiety; iii.)Wherein the index a is an integer from 0 to 2, and each R₆ may beindependently selected from methyl, methoxy, or acetamido moiety. 11.The thiophene azo dye of claim 10, wherein each R₁, R₂ and R₃ isindependently selected from hydrogen, (C₁-C₄)-alkyl, (C₃-C₁₀)-aryl,carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro,(C₁-C₄)-alkyl ester, halogen or amino moiety.
 12. The thiophene azo dyeof claim 1 having a Formula (VIII):A-N═N—X  Formula VIII wherein the A moiety is selected from the groupconsisting of Table 1A Moieties Nos. 1-118 and wherein X is selectedfrom the group consisting of Table 4X Moieties Nos. 1-31.
 13. Thethiophene azo dye of claim 1 having a Formula (VIII):A-N═N—X  Formula VIII wherein the A moiety is selected from the groupconsisting of Table 1A Moieties Nos. 9-11, 15, 23, 34-35, 37-39, 41, 43,47, 50-51, 57-58, 77, 83, 89, 95, 106, and 110-118; and wherein the Xmoiety is selected from the group consisting of Table 4X Moieties Nos.1-31.
 14. The thiophene azo dye of claim 1, said dye having thefollowing formula:

wherein the moiety A is selected from Table 1A Moieties Nos. 1-118; a=0to 2; when a=1 or 2, R₆ is selected from Table 2 R₆ Substituent Identityand Position Nos. 1-40; and R₄ and R₅ grouping is selected from Table 3R₄ and R₅ Groupings Nos. 1-69.
 15. The thiophene azo dye of claim 1,said dye having the following formula:

wherein the moiety A is selected from Table 1A Moieties Nos. 9-11, 15,23, 34-35, 37-39, 41, 43, 47, 50-51, 57-58, 77, 83, 89, 95, 106, and110-118; a=0 to 2; when a=1 or 2, R₆ is selected from Table 2 R₆Substituent Identity and Position Nos. 1, 3, 5, 7, 12, 13, 14, 31, 36and 40; and R₄ and R₅ grouping is selected from Table 3 R₄ and R₅Groupings Nos. 3, 5-6, 10, 13-14, 17, 19-21, 24, 27-28, 31-34, 38, 41,44-48, 52, 54-55, 58, 60-64 and
 69. 16. The thiophene azo dye of claim1, said dye having a formula selected from Table 5 Formula Nos. 1-42.